Contents1 Introduction 1 Review of the Molten Salt and Hydrogen

storage as an example of Energy Storage

1.1 Types of Energy Storage Systems ESS 1 Systems to support Distributed
Generation
2 Molten Salt Storage: 3

2.1 Molten Salt 3 Assignment 1: Energy Storage for

Distributed Generation Application
2.2 Application to enhance solar energy profile EE 805 - Advanced Electric Grids:
4 Operation and Control

3 Hydrogen Storage: 5

3.1 Introduction to hydrogen production 6

3.1.1 Electrolysis of water...................................................................................................................

3.2 Polymer electrolyte fuel cells ( PEFCs), 7

3.3 Limitations of hydrogen as Energy storage

Systems. 10

4 conclusion 11 Ahmad Fawzy

Registration # 20115122
5 References 11
1 INTRODUCTION

Conventional generation depends on rotating additional unrequired power in the grid as (spinning
reserve) to achieve grid proper response to load and generation fluctuation, on the other hand most
distributed generation “especially the units which depend on renewable energy” are unable to inject a
controllable spinning reserve to the grid, which is considered a point of weakness and prohibits large
integration of distributed generation points to the stable conventional network. Electricity generation
from wind and solar power is growing rapidly. However, these technologies present significant
challenges to grid operators, including intermittent output and a mismatch between peak output and peak
demand. Loads can easily exceed the Distributed Generation DG units’ capacity due to Power plants
trips, transmission lines failures, environmental conditions that limits the DG units’ capacity, or a
sudden demand increase which exceeds the unit available generation capacity at a certain time.

Grid-scale Energy Storage Systems ESS(s) enables further growth of these low-emissions renewable
energy generating sources by levelling peak load, increasing the capacity factors of wind and solar
installations, and transforming these intermittent generators into grid-dispatchable resources. A variety
of grid-scale storage technologies are available, including pumped hydro, compressed air, and various
types of battery storage.

Energy Storage Sources available on the network can serve grid operation by: [1]

1- Decrease the amount of required spinning reserve required for grid stability; as it provides
additional energy source to meet the sudden demand until starting of emergency fast starting central
units, this helps to change the reserve allocation strategy to be mainly depending on cold standby
units with enhanced grid operating costs.

2- Energy storage systems can meet peak load demand and substitute the use of fossil fuel units, this
introduce a load levelling preferred option for operation of the central grid.

3- Integrate the use of renewable energy supplies with the grid as reliable full dispatch able sources, as
it controls their intermittent fluctuating power output by providing a mean to store excessive power
at other grid points to be used for matching demand at time of need.

4- Enhance power quality of grids which are heavily dependent on renewables by introducing
measures of stabilizing and control power system variables like grid Volt and Frequency.

5- An investment of competitive initial cost that can be used as a tool for grid private operator to
enhance Energy management and increase financial gain through storage of energy in off-peak
hours with cheap prices and re-selling the stored energy at peak hours with high tariff.

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1.1 Types of Energy Storage Systems ESS
Mechanical Electro-Chemical Electrical Thermal

Pumped Hydro Storage Hydrogen Storage Superconducting magnet Molten Salt Storage

Compressed Air Energy Storage Battery Storage Electrical Double layer Capacitors
Adiabatec Compressed Air Energy
Storage
Flywheel energy storage Super Capacitors

Worldwide operational energy storage technology share

based on installed capacity
(DOE database 2015)

0.01 0.02 0.01 PHS (Pumped Hydro Storage)

other
Battery ESS
Thermal ESS
Flywheel ESS

0.96

Worldwide operational energy storage technology share based on installed capacity (DOE database
2015)

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 Dispersed Storage Units: Massive Energy Storage; Power output versus production time

2 MOLTEN SALT STORAGE:

2.1 Molten Salt

Thermal storage stores energy in the form of heat that is either "sensible" or "latent". Sensible heat
corresponds to thermal storage in a single phase where the temperature of the material varies with the
amount of stored energy. The equation for heat flow from hot to cold is:

Q = m C ΔT

Where Q is the (sensible) heat, m is the mass, C is the specific heat, and ΔT is the temperature
difference. Both liquid (water, oil, molten salt) and solid (rock, metal) media can be used. This requires
insulation to maintain a temperature gradient to store the heat. For low temperature (25  90°C), water
is ideal; it has a relatively high specific heat (4.2 kJ/kg°C), is cheap, and over a 60°C temperature
difference can store 250 kJ/kg. Operating at low temperatures avoids complications associated with the
high vapor pressure and containment.

Latent heat is stored using phase-change materials that take advantage of the (specific) latent heat L
associated with a phase transition: Q = m C ΔT + m L though this is not as efficient at high
temperatures. Phase-change materials are appealing because of their high energy storage density; water,
for example, has a latent heat of fusion 335 kJ/kg which is approximately 80 times the amount of heat
that is required to raise the temperature of 1 kg of water by 1°C. While latent heat may be suitable for a
house with solar panels, additional complications associated with cost and repeated use currently make
sensible heat a better option for large-scale storage.
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Molten salts have high boiling points, low viscosity, low vapor pressure (not easily vapourizing), and
high volumetric heat capacities. A higher heat capacity corresponds to a smaller storage tank volume. In
choosing the chemical mixture, it is advantageous to have the lowest possible melting point (and highest
boiling point) to maximize the available temperature range for the molten salt. If the melting point is too
high, additional heating may be required to prevent freezing.

Salts used for storage systems ESS (such as sodium nitrate NaNO 3 and potassium nitrate KNO3) have
melting points between 300-500°C and volumetric heat capacities between 1670 - 3770 kJ/m 3°C.
Sodium hydroxide NaOH has a melting point of 320°C and can be used up to 800°C, but is highly
corrosive. Commercially available "HITEC" salt used in solar plants consists of potassium nitrate (53%
by weight), sodium nitrite NaNO2 (40% by weight), and sodium nitrate (7% by weight) with a liquid
temperature range of 149 - 538°C.

The salts are heated and stored in an insulating container during off-peak hours. When energy is needed,
the salt is pumped into a steam generator that boils water, spins a turbine, and generates electricity. The
conversion of thermal energy to electricity can proceed by different cycles such as the Rankine, Brayton,
and Air-Brayton cycles.

The cooled salt is pumped back into the storage tank to be heated and reused.

There are two different configurations for the molten salt energy storage system: two-tank direct and
thermocline.

The two-tank direct system, using molten salt as both the heat transfer fluid (absorbing heat from the
reactor or heat exchanger) and the heat storage fluid, consists of a separate hot and cold storage tank.

Figure 1: Thermocline molten salt ESS

The thermocline system (see Figure) uses a single tank such that hot and cold salt are separated by a
vertical temperature gradient (due to buoyancy force) to prevent mixing. There are two cycles in the
thermocline system: charging and discharging. To charge, salt flows out of the cold side, is heated by the

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heat exchanger (reactor), and flows into the tank's hot side. To discharge, salt flow out of the hot side,
transfers heat to generate power (turbine), and flows into the tank's cold side. The thermocline system
reduces costs through a single tank and cheap filler material in the tank to act as thermal storage; the
estimated cost relative to the two-tank direct system is about 35%.

2.2 Application to enhance solar energy profile

Thermal energy storage is currently being used in concentrated solar plants consisting of parabolic
mirrors (troughs) or sun-tracking mirrors (heliostats) that direct sunlight at a focal point receiver tube in
the trough or a single "power tower" where a heat transfer fluid (oils) absorbs the energy. The heated
fluid can be directed to a steam generator for electricity, or a heat exchange can transfer the energy to
molten salts to be stored (with round-trip efficiencies of 95 - 99%). To eliminate this intermediate
exchange in indirect plants, direct plants use molten salt, which operates at low vapor pressure at 500°C,
as the heat transfer fluid; this has the added benefit that molten salts are cheaper and more
environmentally friendly than synthetic oil, but have higher melting points and therefore may require
freeze protection.

Typical plants using molten salt as a heat transfer fluid have a mixture, consisting of 60% sodium nitrate
and 40% potassium nitrate, melts at 220°C. "Cold" molten salt at 260°C is then heated to about 550°C
and stored.

While these plants serve as proof of concept for large-scale molten salt technology, the rarity of
commercial solar thermal storage comes down to cost. This indirect determination overestimates the cost
since it doesn't take into account the ability of thermal storage to sell electricity during peak demand
hours with more revenue.

3 HYDROGEN STORAGE:

Hydrogen energy storage is a process wherein the surplus of energy created by renewables during low
energy demand periods is used to power electrolysis, a process in which an electrical current is passed
through a chemical solution in order to separate hydrogen. Once hydrogen is created through electrolysis
it can be used in stationary fuel cells, for power generation, to provide fuel for fuel cell vehicles, injected
into natural gas pipelines to reduce their carbon intensity, or even stored as a compressed gas, cryogenic
liquid or wide variety of loosely-bonded hydride compounds for later use. Hydrogen created through
electrolysis is showing great promise as an economic fuel choice, with data from the International
Energy Agency predicting that hydrogen generated from wind will be cheaper than natural gas by
2030.[3]

However our interest in this report is introducing hydrogen electricity generation by fuel cells concept
rather than as a gas fuel source as it is more suitable to the desired application of having more grid
control of fast acting energy storage systems, although there is a potential of using fuel hydrogen storage
for weekly storage reservoirs as a form of Distributed generation continuously running source.

Regenerative hydrogen fuel cells (RHFC’s) have several characteristics that are well-suited to large-
scale energy storage.

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 1- They are not subject to geological requirements, which are important restrictions on pumped
hydro and compressed air storage.
2- The energy capacity and power capacity of a regenerative fuel cell can be configured
independently.
3- Storing energy in hydrogen provides a dramatically higher energy density than any other energy
storage medium.
4- Hydrogen is also a flexible energy storage medium which can be used in stationary fuel cells
(electricity only or combined heat and power), internal combustion engines, or fuel cell vehicles.
5- Hydrogen storage has a very low rate of self-discharge, and has therefore been proposed for
seasonal storage.
6- The cost of energy storage in a regenerative hydrogen fuel cell is already potentially competitive
with batteries in an optimized energy arbitrage system.

The most common configuration among existing

systems contains an alkaline water electrolyzer (AWE)
and a polymer electrolyte membrane fuel cell
(PEMFC).

3.1 Introduction to hydrogen production

3.1.1 Electrolysis of water

Alkaline water electrolysis is one of the easiest methods for hydrogen production although it is relatively

expensive technology. If relatively small quantities of hydrogen are required, on-site electrolysis of
water may result more economical than other methods. This technique is very clean and produces more
than 99.989% purity of hydrogen gas. In addition, electrolysis can be linked to renewable electricity-
producing technologies and hence could become even more important in the DG storage applications.
Usually an alkaline medium is employed (25–30% KOH). The electrolytic reactions that occur on each
electrode are given by the following equations:

(3.10a) Cathode: 2H2O + 2e− → 2OH− + H2 (3.10b) Anode: 2OH− → ½O2 + H+ + 2e−

(3.10c) Overall: H2O → H2 + ½O2

Cell voltage is directly proportional to the power consumption for the process because the current
efficiency for alkaline electrolysis is very close to 100%. Generally, this cell voltage is composed of:

(3.11) E = Erev + ηa + ηc + ηohm

where Erev refers to the reversible thermodynamic decomposition voltage, ηa to the anode over potential,

ηc to the cathode over potential and ηohm to the inter-electrode ohmic drop.

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Present-day electrolysis have a cell voltage of 1.8–2.2 V and operate between 343 K (70 C) and 363 K
(90 C), which means voltage efficiency from 68% to 80% only. To increase this efficiency, the voltage
should be reduced by lowering the over voltages experienced (at the cathode and anode) and the inter
electrode resistance from the electrolyte, the membrane and the bubbles.

The cell voltage increases when the process is operated at higher current densities. Above a current
density of 150 mA/cm2, this increment is mainly due to the higher bubble population in the electrolyte as
the gas production rate increases linearly with current density. Therefore, to lower the internal ohmic
drop, the bubble residence time in the inter-electrode gap has to be minimized.

This residence time is dependent on the characteristic bubble size as it influences the drag and buoyancy
force of the bubble movement. The characteristic size itself is dependent on the cell configuration (such
as cell and electrode geometry) and operational parameter (such as current density, electrolyte flow
conditions, temperature and pressure).

3.1.2 Polymer electrolyte fuel cells ( PEFCs),

Also known as Proton-exchange membrane fuel cells

(PEMFC). Proton exchange membrane fuel cell
transforms the chemical energy liberated during the
electrochemical reaction of hydrogen and oxygen to
electrical energy, as opposed to the direct combustion of
hydrogen and oxygen gases to produce thermal energy.

A stream of hydrogen is delivered to the anode side of

the Membrane Electrode Assembly MEA. At the anode
side it is catalytically split into protons and electrons.
This oxidation half-cell reaction or hydrogen oxidation
reaction (HOR) is represented by: At the anode:

The newly formed protons permeate through the polymer electrolyte membrane to the cathode side. The
electrons travel along an external load circuit to the cathode side of the Membrane Electrode Assembly
MEA, thus creating the current output of the fuel cell. Meanwhile, a stream of oxygen is delivered to the
cathode side of the MEA. At the cathode side oxygen molecules react with the protons permeating
through the polymer electrolyte membrane and the electrons arriving through the external circuit to form
water molecules. This reduction half-cell reaction or oxygen reduction reaction (O/R Reaction) is
represented by:

At the cathode:

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Overall reaction:

The reversible reaction is expressed in the equation and shows the reincorporation of the hydrogen
protons and electrons together with the oxygen molecule and the formation of one water molecule. The
potentials in each case are given with respect to the standard hydrogen electrode.

Figure 2: Schematic presentation of the cross-section of a single polymer electrolyte fuel cell (PEFC).
The "heart" of the cell, which is magnified in the scheme, is the so-called membrane-electrode assembly
MEA. In its simplest form, the "electrode" component of the M&E assembly would be a thin film (5-50
m thick) containing dispersed Platinum (Pt) catalyst. This catalyst layer is in good contact with an
ionomeric membrane, the central slab in the scheme in figure 2 shown in green, which serves as the
electrolyte and the gas separator in the cell. The ionomeric membrane electrolyte is typically 50-175 m
thick1.

A so-called M&E assembly thus consists of an ionomeric membrane with thin catalyst layers bonded
onto each of its two surfaces. It can be seen that the M&E assembly has the generic structure of an

1
An ionomer (/ ˌaɪˈɑːnəmər /) (iono- + -mer) is a polymer composed of repeat units of both electrically neutral
repeating units and ionized units covalently bonded to the polymer backbone as pendant group moieties. Usually
no more than 15 mole percent are ionized. The ionized units are often carboxylic acid groups.
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electrochemical cell: electrode/electrolyte/electrode, packaged in the form of a sandwich of three thin
films. The "gas-diffuser" (or "backing") layers in immediate contact with the catalyzed membrane ( see
figure – light blue layer) are made of hydro-phobized porous carbon paper, or carbon cloth. These
layers are typically 100-300 m thick and are wet-proofed by treatment with poly-tetrafluoroethylene
(PTFE). The role of these gas diffusers is to enable direct and uniform access of the reactant gases,
hydrogen and oxygen, to the catalyst layers, without having to diffuse through films of liquid water.

The single cell is completed by current collector plates which usually contain machined flow fields, as
required for effective distribution of reactant gases along the surfaces of the electrodes. These plates,
traditionally made of high density graphite, become bipolar plates in the fuel cell stack, in which case
they would have gas flow fields on both sides, as shown schematically in Figure 2. A general view of a
single cell hardware is presented in Figure 3. The Teflon masks shown are gaskets that confine the gas
flow to the active area and provide, together with the periphery of the ionomeric membrane, an effective
seal. In a fuel cell stack, many such cells are stacked together to generate the voltage required for a
given application, since a single hydrogen/oxygen fuel cell operated at only about 0.7V.

FIGURE 3 – Single fuel cell Hardware illustration

The above short discussion of the unit cell of a polymer electrolyte fuel cell stack, highlights different
materials of unique characteristics ( see italicized materials & components names) , required to achieve a
fuel cell power source of high performance, high energy conversion efficiency and stable long-term
operation. We discuss them further below.

Electrocatalysts: Returning to the M&E assembly, the magnified part in Figure 2 highlights the central
element of the PEFC which consists of a proton-conducting membrane electrolyte with a composite
catalyst layer adjacent to each of its surfaces. The scheme shows the catalyst layer as Pt (small circles)
supported on carbon (larger circles). This type of catalyst has been used in more recent developments of
PEFCs. The Pt/C powder, prepared mostly by procedures based on colloid chemistry consists of Pt
particles about 2 nm in diameter, supported on carbon particles about 10 nm in diameter. Pt is an
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essential catalyst for the electrochemical conversion of hydrogen and oxygen at the anode and cathode
of the fuel cell, respectively, into electric current (electric power).

The Pt/C powder has to be intimately intermixed with recast ionomer to provide sufficient ionic
conductivity within the catalyst layer. Thus, the catalyst layer can be described as a Pt/C//ionomer
composite, where each of the three components are uniformly distributed within the volume of the layer.
PEFC stacks fabricated at this point still use PTFE-bonded Pt black catalysts applied by hot-press to the
ionomeric membrane. Such Pt-black- based catalyst layers typically require a Pt loading 20-40 times
higher than that required in the Pt/C catalyst ( 4mgPt/cm 2 vs. 0.1 mg Pt/cm2) to obtain a similar cell
performance. Pt/C catalysts will have to be adapted in commercial PEFCs because of their much lower
cost and their intrinsic high performance and reliability. Work at LANL during the last five years has
brought the low-Pt- loading M&E technology to the point of industrial realization, enabling an important
lowering of the cost barrier to implementation of polymer electrolyte fuel cell technology.

The Gas Diffuser: The porous backing layer which is placed behind the catalyst layer (figure 2) fulfills
important tasks in the Polymer Electrolyte Fuel cell PEFC. In this layer, combined requirements of
effective reactant gas supply to the catalyst layer and effective water supply and removal in either vapor
or liquid form have to be simultaneously fulfilled. Wet-proofing by Poly Tetra Fluoro Ethylene PTFE film
is required to ensure that at least part of the pore volume in the cathode backing remains free of liquid
water in an operating cell, so as to enable rapid gas-phase transport. The scale of the porosity and the
amount of PTFE added are two important parameters that determine the success of the backing layer in
fulfilling the combined tasks of gas and water transport. Obviously, the backing layer has to be made of
a material of high and stable electronic conductivity in a wet environment. Although some expanded
metal structures have been suggested, most of PEFC backings to date have been based on porous carbon
paper or cloth.

Strengths and Weaknesses of Polymer Electrolyte Membrane Fuel Cells:

The PEMFC is a prime candidate for vehicle and other mobile applications of all sizes down to mobile
phones, because of its compactness. But Fuel Cells based on PEM still have many issues:

1. Water management

Water management is crucial to performance: if water is evaporated too slowly, it will flood the
membrane and the accumulation of water inside of field flow plate will impede the flow of oxygen into
the fuel cell, but if water evaporates too fast, the membrane will dry and the resistance across it
increases. Both cases will cause damage to stability and power output. Water management is a very
difficult subject in PEM systems, primarily because water in the membrane is attracted toward the
cathode of the cell through polarization.

2. Vulnerability of the Catalyst

The platinum catalyst on the membrane is easily poisoned by carbon monoxide (no more than one part
per million is usually acceptable) and the membrane is sensitive to things like metal ions, which can be
introduced by corrosion of metallic bipolar plates, metallic components in the fuel cell system or from
contaminants in the fuel/oxidant.
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3.2 Limitations of hydrogen as Energy storage Systems.
Energy storage have an important role in integrating intermittent renewable energy generation into the
electric grid, including capturing over-generation (‘‘spilled power’’) for later use.

In the case of a hydrogen system using a 350 bar compressed gas storage, one can expect a round trip
efficiency of only 47%. If one allows for the use of heat released during the conversion of hydrogen
back to electricity in a fuel cell on site, the overall energy efficiency can be increased to 66%.

The low round-trip efficiency of hydrogen storage suggests that building this type of storage will always
result in a less favorable net energy outcome than other technology options with higher round-trip
efficiencies. However, in some situations, its low round-trip efficiency is offset by:

1- Higher ESOIe ratio “The ESOIe ratio is a measure of how much energetic benefit our society
receives in exchange for each unit of energy invested in building an energy storage system”, and
2- High energy return on investment “cost wise” (EROI) of the technology.

4 CONCLUSION

Comparison of the molten Salt versus Hydrogen Storage technologies as candidates for “ESS” to
support distributed generation in power grids shows the following

Comparison Aspect Molten Salt Hydrogen Storage (Fuel Cells)

Round trip efficiency
Batteries range
(Lithium ion 95%)
Maximum Power rating
Round trip efficiency >80% is
estimated as conversion is done
once from Heat to steam power,
accounting for thermal losses
only.[6]
Till 150 MW
Hydrogen electrolysis efficiency
is about 75%, fuel cell
efficiency ranges to 60%, total
round trip efficiency is no
greater than 45%
Till 100 MW

100 MW
Startup time Minutes to less than an hour, Seconds to less than a minute,
most suitable to be online unit Can serve as emergency start
to level the demand by peak unit
shaving.
Energy density / unit volume 70 – 210 Watt.hr per liter 600 Watt.hr per liter (at 200bar)

(Li-ion 200-400 Watt.hr per

liter)
Initial cost per Storage capacity Low cost , 33 times cheaper High cost, typical low cost
than Li-ion Batteries values $434/kW
Running cost Low running cost Average 0.25 $ / kW.hr
Life time Reaching 30 years 5 – 30 years
Operations simplicity Similar to Thermal units, New technology, Needs
moderate advanced Knowledge and
precautions due to presence of

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 Highly flammable material.
O&M Costs $20/kW-yr
Despite being less efficient, Hydrogen storage and reuse at fuel cell is a more promising field due to the
following aspects.

1- Depends on electrical sources for energy storage rather than heat energy, any renewable produce
direct electrical heat from natural sources.
2- Fast startup and moderate temperature makes it suitable for portable application and integration
with small sizes system, as it has higher energy density for unit volume.
3- Storage material can be easily transferred from production centers to utilization centers, not true
for molten salt.
4- Byproducts of energy production are environmental friendly (heat and water).

Managing the risks of using hydrogen gas as a highly explosive substances will promote the use of this
technology fast and to a different scale.

5 REFERENCES

[1] Energy Management of Distributed Generation Systems - Lucian Mihet-Popa

[2] Energy Environ. Sci., 2015, 8, 1938. Hydrogen or batteries for grid storage? A net energy
analysis Matthew A. Pellow,*a Christopher J. M. Emmott,bc Charles J. Barnhartd and Sally M.
Bensonaef

[3] Molten Salt Storage -John Dodaro, December 15, 2015. Submitted as coursework for PH240,
Stanford University, Fall 2015

[4] R.M. Navarro, ... J.L.G. Fierro, in Compendium of Hydrogen Energy, 2015

[5] The Polymer Electrolyte Fuel Cell: Materials Issues in a Hydrogen Fueled Power Source.
Shimshon Gottesfeld, Materials Science and Technology Division. Electronic and Electrochemical
Materials & Devices Group

[6] Hameer, Sameer & Van Niekerk, Johannes. (2016). Thermodynamic Modelling of Thermal
Energy Storage Systems. Energy Procedia. 93. 10.1016/j.egypro.2016.07.145.

[7] Electricity storage and renewables: costs and markets to 2030, IRENA 2017

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